Photosensitive resin composition, photosensitive element, printed wiring board, and method for manufacturing the printed wiring board.

Abstract

One aspect of this disclosure relates to a photosensitive resin composition comprising (A) an acid-modified vinyl resin, (B) a thermosetting resin, (C) a photopolymerization initiator, (D) a photopolymerization compound, and (E) an elastomer, wherein (B) the thermosetting resin comprises a bisphenol-type epoxy compound with an average molecular weight of less than 360, and (E) the elastomer comprises an acrylic elastomer.

Description

Technical Field

[0001] The present disclosure relates to a photosensitive resin composition, a photosensitive element, a printed wiring board, and a method for manufacturing the printed wiring board. Prior Art

[0002] In the field of printed wiring boards, a process for forming a permanent resist on printed wiring boards is used. This permanent resist prevents corrosion of the conductive layer and maintains electrical insulation between conductive layers during use of the printed wiring board. In recent years, permanent resist has also been used as a solder resist film during processes such as flip-chip mounting and wire bonding of semiconductor devices on printed wiring boards using solder, preventing solder from adhering to unwanted portions of the conductive layer of the printed wiring board.

[0003] Conventionally, permanent resists have been produced by screen printing with thermosetting resin compositions or by photographic methods using photosensitive resin compositions. For example, in flexible wiring boards using mounting methods such as FC (Flip Chip), TAB (Tape Automated Bonding), and COF (Chip on Film), a permanent resist is formed by screen printing a thermosetting resin paste and then heat-curing it, except for the IC chip, electronic components, LCD (Liquid Crystal Display) panel, and the connecting wiring pattern (see, for example, Patent Document 1).

[0004] In semiconductor package substrates such as BGA (Ball Grid Array) and CSP (Chip Size Package) mounted on electronic parts, it is necessary to remove the permanent resist at the bonding portion (1) in order to flip-chip mount the semiconductor element on the semiconductor package substrate via solder, (2) in order to wire-bond the semiconductor element to the semiconductor package substrate, or (3) in order to solder the semiconductor package substrate to the motherboard. In the formation of the image of the permanent resist, a photographic method is used in which a photosensitive resin composition is applied and dried, and then selectively irradiated with active light such as ultraviolet rays to cure it, and then developed to remove only the unirradiated portion to form an image. Photolithography is widely used in the electronic materials industry for the formation of images of photosensitive materials because of its good workability and suitability for mass production. (For example, see Patent Document 2).

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2003-198105 [Patent Document 2] Japanese Patent Application Laid-Open No. 2011-133851

[0006] As printed wiring boards become increasingly dense, permanent resists (solder resists) are being required to achieve even higher performance. In particular, demands for fine pattern formation, heat resistance, and thermal shock resistance are increasing year by year, making it crucial to achieve a high level of balance between these characteristics. Summary of the Invention

[0007] The present disclosure aims to provide a photosensitive resin composition capable of forming a permanent resist having excellent resolution and pattern forming properties and excellent heat resistance and thermal shock resistance, a photosensitive element using the photosensitive resin composition, a printed wiring board, and a method for producing a printed wiring board.

[0008] One aspect of the present disclosure relates to a photosensitive resin composition comprising (A) an acid-modified vinyl-containing resin, (B) a thermosetting resin, (C) a photopolymerization initiator, (D) a photopolymerizable compound, and (E) an elastomer, wherein the thermosetting resin (B) comprises a bisphenol-type epoxy compound having an average molecular weight of 360 or less, and the elastomer (E) comprises an acrylic elastomer.

[0009] Another aspect of the present disclosure is related to a photosensitive element comprising a support film and a photosensitive layer formed on the support film, wherein the photosensitive layer comprises the above-mentioned photosensitive resin composition.

[0010] Another aspect of the present disclosure relates to a printed wiring board having a permanent resist comprising a cured product of the photosensitive resin composition.

[0011] Another aspect of the present disclosure relates to a method for manufacturing a printed wiring board, which comprises a process of forming a photosensitive layer on a substrate using the above-mentioned photosensitive resin composition or photosensitive element, a process of exposing and developing the photosensitive layer to form a resist pattern, and a process of curing the resist pattern to form a permanent resist. [Effects of the Invention]

[0012] According to the present disclosure, a photosensitive resin composition capable of forming a permanent resist having excellent resolution and pattern forming properties and excellent heat resistance and thermal shock resistance, a photosensitive element using the photosensitive resin composition, a printed wiring board, and a method for manufacturing a printed wiring board can be provided. Simple diagram description

[0013] FIG1 is a cross-sectional view schematically showing a photosensitive element according to this embodiment. Implementation Method

[0014] One aspect of the present disclosure relates to the following photosensitive resin composition, photosensitive element, printed wiring board, and method for manufacturing the printed wiring board. [1] A photosensitive resin composition comprising (A) an acid-modified vinyl-containing resin, (B) a thermosetting resin, (C) a photopolymerization initiator, (D) a photopolymerizable compound, and (E) an elastomer, wherein the thermosetting resin comprises a bisphenol-type epoxy compound having an average molecular weight of 360 or less, and the elastomer comprises an acrylic elastomer. [2] The photosensitive resin composition as described in [1] above, wherein The content of the thermosetting resin is 5 to 25% by mass based on the total solid content of the photosensitive resin composition. [3] The photosensitive resin composition as described in [1] or [2] above, wherein The acrylic elastomer has a carboxyl group. [4] The photosensitive resin composition as described in [3] above, wherein The acrylic elastomer further has an n-butyl group. [5] The photosensitive resin composition as described in any one of [1] to [4] above, wherein The weight average molecular weight of the acrylic elastomer is 5,000 to 20,000. [6] The photosensitive resin composition described in any one of [1] to [5] above, further comprising (I) a silane coupling agent. [7] The photosensitive resin composition as described in any one of [1] to [6] above, further comprising (F) an inorganic filler. [8] A photosensitive element comprising a support film and a photosensitive layer formed on the support film, wherein the photosensitive layer comprises the photosensitive resin composition described in any one of [1] to [7]. [9] A printed wiring board comprising a permanent resist comprising a cured product of the photosensitive resin composition described in any one of [1] to [7].

[10] A method for manufacturing a printed wiring board, comprising: A process of forming a photosensitive layer on a substrate using the photosensitive resin composition described in any one of items [1] to [7] above; a process of exposing and developing the aforementioned photosensitive layer to form a resist pattern; and a process of curing the aforementioned resist pattern to form a permanent resist.

[11] A method for manufacturing a printed wiring board, comprising: The process of forming a photosensitive layer on a substrate using the photosensitive element described in [8] above; the process of exposing and developing the aforementioned photosensitive layer to form a resist pattern; and the process of curing the aforementioned resist pattern to form a permanent resist.

[0015] The present disclosure is described in detail below. In this specification, the term "process" includes not only independent processes, but also processes that cannot be clearly distinguished from other processes as long as the intended effect of the process is achieved. Regarding the term "layer", when observed in a plan view, in addition to the structure of the shape formed on the entire surface, it also includes the structure of the shape formed on a part. The numerical range represented by "~" represents a range that includes the numerical values ​​recorded before and after "~" as the minimum and maximum values, respectively. Within the numerical range recorded in stages in this specification, the upper limit or lower limit of the numerical range of any stage can also be replaced by the upper limit or lower limit of the numerical range of other stages. Within the numerical range recorded in this specification, the upper limit or lower limit of its numerical range can be replaced by the value shown in the embodiment.

[0016] In this specification, when the amount of each component in a composition is mentioned, or when multiple substances corresponding to each component are present in a composition, unless otherwise specified, the amount refers to the total amount of the multiple substances present in the composition.

[0017] In this specification, the term "(meth)acrylate" refers to at least one of "acrylate" and its corresponding "methacrylate." The same applies to other similar expressions such as (meth)acrylic acid and (meth)acryloyl. In this specification, the term "solids" refers to the non-volatile components other than volatile substances (such as water and solvent) contained in the photosensitive resin composition, and also includes components that are liquid, syrupy, or waxy at room temperature (approximately 25°C).

[0018] [Photosensitive resin composition] The photosensitive resin composition of this embodiment contains (A) an acid-modified vinyl-containing resin, (B) a thermosetting resin, (C) a photopolymerization initiator, (D) a photopolymerizable compound, and (E) an elastomer as essential components. The photosensitive resin composition of this embodiment is a negative-working photosensitive resin composition, and the cured film of the photosensitive resin composition is suitable for use as a permanent resist. The following describes the components used in the photosensitive resin composition of this embodiment in more detail.

[0019] (Component (A): Acid-modified vinyl-containing resin) The photosensitive resin composition of this embodiment includes an acid-modified vinyl-containing resin as component (A). The acid-modified vinyl-containing resin is not particularly limited as long as it has a vinyl bond as a photopolymerizable ethylenically unsaturated bond and an alkali-soluble acidic group.

[0020] Examples of groups having ethylenically unsaturated bonds in component (A) include vinyl, allyl, propargyl, butenyl, ethynyl, phenylethynyl, maleimide, naphthaleneimide, and (meth)acryloyl groups. Among these, (meth)acryloyl groups are preferred from the perspectives of reactivity and resolution. Examples of acidic groups in component (A) include carboxyl, sulfo, and phenolic hydroxyl groups. Among these, carboxyl groups are preferred from the perspective of resolution.

[0021] The component (A) is preferably an acid-modified vinyl-containing epoxy derivative obtained by reacting (a) an epoxy resin (hereinafter sometimes referred to as "component (a)"), (b) an organic acid containing an ethylenically unsaturated group (hereinafter sometimes referred to as "component (b)"), and (c) a polybasic acid anhydride containing a saturated or unsaturated group (hereinafter sometimes referred to as "component (c)").

[0022] Examples of acid-modified vinyl-containing epoxy derivatives include acid-modified epoxy (meth)acrylates. Acid-modified epoxy (meth)acrylates are resins obtained by acid-modifying epoxy (meth)acrylate, the reaction product of components (a) and (b), with component (c). Examples of acid-modified epoxy (meth)acrylates include those obtained by adding a saturated or unsaturated polybasic acid anhydride to an esterified product obtained by reacting an epoxy resin with a vinyl-containing monocarboxylic acid.

[0023] Examples of the component (A) include an acid-modified vinyl-containing resin (A1) (hereinafter sometimes referred to as "component (A1)") obtained by using a bisphenol novolac-type epoxy resin (a1) (hereinafter sometimes referred to as "epoxy resin (a1)") as the component (a), and an acid-modified vinyl-containing resin (A2) (hereinafter sometimes referred to as "component (A2)") obtained by using an epoxy resin (a2) other than the epoxy resin (a1) (hereinafter sometimes referred to as "epoxy resin (a2)") as the component (a).

[0024] Examples of the epoxy resin (a1) include epoxy resins having a structural unit represented by the following formula (I) or (II).

[0025] [Chemistry 1]

[0026] In formula (I), R represents a hydrogen atom or a methyl group. Multiple Rs may be the same or different. Y and Y each independently represent a hydrogen atom or a glycidyl group, and at least one of Y and Y is a glycidyl group. From the perspective of suppressing undercuts and improving the linearity and resolution of the resist pattern profile, R is preferably a hydrogen atom. From the perspective of further improving thermal shock resistance, Y and Y are preferably glycidyl groups.

[0027] The number of structural units represented by formula (I) in the epoxy resin (a1) is 1 or greater, and can be 10-100, 12-80, or 15-70. When the number of structural units is within this range, the linearity of the resist pattern contour, adhesion to the copper substrate, heat resistance, and electrical insulation properties are easily improved. Here, the number of structural units in a single molecule represents an integer value, and in an aggregate of multiple molecules, represents an average value, i.e., a rational number. The same applies to the number of structural units in the following descriptions.

[0028] [Chemistry 2]

[0029] In formula (II), R<12> represents a hydrogen atom or a methyl group. Multiple R<12> groups may be the same or different. Y<3> and Y<4> each independently represent a hydrogen atom or a glycidyl group, and at least one of Y<3> and Y<4> is a glycidyl group. From the perspective of suppressing undercuts and improving the linearity and resolution of the resist pattern profile, R<12> is preferably a hydrogen atom. From the perspective of further improving thermal shock resistance, Y<3> and Y<4> are preferably glycidyl groups.

[0030] The number of structural units represented by formula (II) in the epoxy resin (a1) is 1 or more, and can be 10 to 100, 12 to 80, or 15 to 70. When the number of structural units is within the above range, the linearity of the resist pattern contour, the adhesion to the copper substrate, and the heat resistance are easily improved.

[0031] In formula (II), an epoxy resin in which R 12 is a hydrogen atom and Y 3 and Y 4 are glycidyl groups is commercially available as the EXA-7376 series (manufactured by DIC Corporation, product name), and an epoxy resin in which R 12 is a methyl group and Y 3 and Y 4 are glycidyl groups is commercially available as the EPON SU8 series (manufactured by Mitsubishi Chemical Corporation, product name).

[0032] The epoxy resin (a2) is not particularly limited as long as it is an epoxy resin different from the epoxy resin (a1). From the perspective of suppressing the generation of undercuts and improving the linearity of the resist pattern contour, the adhesion to the copper substrate, and the resolution, it is preferably at least one selected from the group consisting of novolac-type epoxy resins, bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, trisphenol methane-type epoxy resins, and biphenyl-type epoxy resins.

[0033] Examples of novolac-type epoxy resins include epoxy resins having a structural unit represented by the following formula (III). Examples of bisphenol A-type epoxy resins or bisphenol F-type epoxy resins include epoxy resins having a structural unit represented by the following formula (IV). Examples of trisphenol methane-type epoxy resins include epoxy resins having a structural unit represented by the following formula (V). Examples of biphenyl-type epoxy resins include epoxy resins having a structural unit represented by the following formula (VI).

[0034] As the epoxy resin (a2), a novolac-type epoxy resin having a structural unit represented by the following formula (III) is preferred. Examples of novolac-type epoxy resins having such a structural unit include a novolac-type epoxy resin represented by the following formula (III').

[0035] [Chemistry 3]

[0036] In formulas (III) and (III'), R represents a hydrogen atom or a methyl group, Y represents a hydrogen atom or an epoxypropyl group, and at least one of the Ys is an epoxypropyl group. In formula (III'), n is 1 or greater, and multiple Rs and Ys may be the same or different. From the perspective of suppressing undercuts and improving the linearity and resolution of the resist pattern outline, R is preferably a hydrogen atom.

[0037] From the perspective of suppressing undercuts and improving the linearity and resolution of the resist pattern outline, the molar ratio of Y5 (a hydrogen atom) to Y5 (a glycidyl group) in formula (III') can be 0 / 100 to 30 / 70 or 0 / 100 to 10 / 90. n1 is 1 or greater, but can also be 10 to 200, 20 to 150, or 30 to 100. When n1 is within the above ranges, the linearity of the resist pattern outline, adhesion to the copper substrate, and heat resistance can be easily improved.

[0038] Examples of the novolac-type epoxy resin represented by formula (III') include phenol novolac-type epoxy resins and cresol novolac-type epoxy resins. These novolac-type epoxy resins can be obtained by reacting a phenol novolac resin or a cresol novolac resin with epichlorohydrin using a known method.

[0039] As the phenol novolac type epoxy resin or cresol novolac type epoxy resin represented by formula (III'), for example, YDCN-701, YDCN-702, YDCN-703, YDCN-704, YDCN-704L, YDPN-638, YDPN-602 (products of NIPPON STEEL Chemical & Material Co., Ltd.), DEN-431, DEN-439 (products of The Dow Chemical Company), EOCN-120, EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1012, EOCN-1025, EOCN-1027, BREN (products of Nippon Kayaku Co., Ltd., product names), EPN-1138, EPN-1235, EPN-1299 (all manufactured by BASF, product names), N-730, N-770, N-865, N-665, N-673, VH-4150, VH-4240 (all manufactured by DIC Corporation, product names), etc.

[0040] Preferred examples of the epoxy resin (a2) include bisphenol A epoxy resins or bisphenol F epoxy resins having a structural unit represented by the following formula (IV). Examples of epoxy resins having such a structural unit include bisphenol A epoxy resins or bisphenol F epoxy resins represented by the following formula (IV').

[0041] [Chemistry 4]

[0042] In formulas (IV) and (IV'), R 14 represents a hydrogen atom or a methyl group. Plural R 14 groups may be the same or different. Y 6 represents a hydrogen atom or a glycidyl group. In formula (IV'), n 2 represents a number of 1 or greater. When n 2 is 2 or greater, plural Y 6 groups may be the same or different, and at least one Y 6 group is a glycidyl group.

[0043] From the perspective of suppressing undercuts and improving the linearity and resolution of the resist pattern profile, R<14> is preferably a hydrogen atom, and from the perspective of further improving thermal shock resistance, Y<6> is preferably a glycidyl group. n<2> represents 1 or greater, but may also be 10-100, 12-80, or 15-60. When n<2> is within the above ranges, the linearity of the resist pattern profile, adhesion to the copper substrate, and heat resistance are easily improved.

[0044] The bisphenol A epoxy resin or bisphenol F epoxy resin in which Y 6 in formula (IV) is a glycidyl group can be obtained by reacting the hydroxyl group (—OY 6 ) of the bisphenol A epoxy resin or bisphenol F epoxy resin in which Y 6 in formula (IV) is a hydrogen atom with epichlorohydrin.

[0045] To promote the reaction between hydroxyl groups and epichlorohydrin, it is best to conduct the reaction in a polar organic solvent such as dimethylformamide, dimethylacetamide, or dimethylsulfoxide in the presence of an alkali metal hydroxide at a reaction temperature of 50-120°C. When the reaction temperature is within this range, the reaction will not become excessively slow, and side reactions can be suppressed.

[0046] Examples of the bisphenol A-type epoxy resin or bisphenol F-type epoxy resin represented by formula (IV') include commercially available products such as jER807, jER815, jER825, jER827, jER828, jER834, jER1001, jER1004, jER1007, and jER1009 (all manufactured by Mitsubishi Chemical Corporation), DER-330, DER-301, and DER-361 (all manufactured by The Dow Chemical Company), and YD-8125, YDF-170, YDF-175S, YDF-2001, YDF-2004, and YDF-8170 (all manufactured by NIPPON STEEL Chemical & Material Co., Ltd.).

[0047] Preferred examples of the epoxy resin (a2) include trisphenolmethane epoxy resins having a structural unit represented by the following formula (V). Examples of trisphenolmethane epoxy resins having such a structural unit include trisphenolmethane epoxy resins represented by the following formula (V').

[0048] [Chemistry 5]

[0049] In formulas (V) and (V'), Y7 represents a hydrogen atom or an epoxypropyl group. Multiple Y7 groups may be the same or different, and at least one Y7 group is an epoxypropyl group. In formula (V'), n3 represents a number of 1 or greater.

[0050] From the perspective of suppressing undercuts and upper defects and improving the linearity and resolution of the resist pattern outline, the molar ratio of Y7 (a hydrogen atom) to Y7 (a glycidyl group) in Y7 can be 0 / 100 to 30 / 70. This molar ratio indicates that at least one of Y7 is a glycidyl group. n3 is 1 or greater, but can also be 10-100, 12-80, or 15-70. When n3 is within the above range, the linearity of the resist pattern outline, adhesion to the copper substrate, and heat resistance are easily improved.

[0051] As the trisphenol methane type epoxy resin represented by formula (V′), for example, FAE-2500, EPPN-501H, and EPPN-502H (all manufactured by Nippon Kayaku Co., Ltd., product names) are commercially available.

[0052] As the epoxy resin (a2), a biphenyl type epoxy resin having a structural unit represented by the following formula (VI) is preferably used. As a biphenyl type epoxy resin having such a structural unit, for example, a biphenyl type epoxy resin represented by the following formula (VI') is used.

[0053] [Chemistry 6]

[0054] In formulas (VI) and (VI'), Y 8 represents a hydrogen atom or an epoxypropyl group. Multiple Y 8 groups may be the same or different, and at least one Y 8 group is an epoxypropyl group. In formula (VI'), n 4 represents a number of 1 or greater.

[0055] Examples of the biphenyl-type epoxy resin represented by formula (VI') include commercially available NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, and CER-3000-L (all manufactured by Nippon Kayaku Co., Ltd.).

[0056] As the epoxy resin (a2), at least one selected from the group consisting of a novolac-type epoxy resin having a structural unit represented by formula (III), a bisphenol A-type epoxy resin having a structural unit represented by formula (IV), and a bisphenol F-type epoxy resin having a structural unit represented by formula (IV) is preferred, and a bisphenol F-type epoxy resin having a structural unit represented by formula (IV) is more preferred.

[0057] From the viewpoint of further improving thermal shock resistance, warpage reduction, and resolution, a bisphenol novolac-type epoxy resin having a structural unit represented by formula (II) can be used as the (A1) component of the epoxy resin (a1), and a bisphenol A-type epoxy resin or a bisphenol F-type epoxy resin having a structural unit represented by formula (IV) can be used in combination as the (A2) component of the epoxy resin (a2).

[0058] Examples of component (b) include acrylic acid, acrylic acid dimers, methacrylic acid, β-furfuryl acrylic acid, β-styryl acrylic acid, cinnamic acid, crotonic acid, and α-cyanocinnamic acid derivatives; half-ester compounds resulting from the reaction of a hydroxyl group-containing (meth)acrylate with a dibasic acid anhydride; and half-ester compounds resulting from the reaction of a vinyl group-containing monoglycidyl ether or a vinyl group-containing monoglycidyl ester with a dibasic acid anhydride. Component (b) may be used alone or in combination of two or more.

[0059] The half ester compound is obtained, for example, by reacting a hydroxyl group-containing (meth)acrylate, a vinyl group-containing monoglycidyl ether, or a vinyl group-containing monoglycidyl ester with a dibasic acid anhydride.

[0060] Examples of the hydroxyl group-containing (meth)acrylates, vinyl group-containing monoglycidyl ethers, and vinyl group-containing monoglycidyl esters include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and glycidyl (meth)acrylate.

[0061] Examples of the dibasic acid anhydride include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, and itaconic anhydride.

[0062] In the reaction between components (a) and (b), the epoxy groups of component (a) are preferably reacted at a ratio of 0.6 to 1.05 equivalents of component (b) per 1 equivalent, and more preferably at a ratio of 0.8 to 1.0 equivalents. This reaction ratio tends to increase photosensitivity and improve the linearity of the resist pattern outline.

[0063] Components (a) and (b) can be dissolved in an organic solvent and reacted. Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; glycol ethers such as methyl celulose, butyl celulose, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, and triethylene glycol monoethyl ether; esters such as ethyl acetate, butyl acetate, butyl celulose acetate, and carbitol acetate; aliphatic hydrocarbons such as octane and decane; and petroleum-based solvents such as petroleum ether, naphtha, hydrogenated naphtha, and solvent naphtha. These organic solvents may be used alone or in combination of two or more.

[0064] A catalyst may be used to promote the reaction between component (a) and component (b). Examples of the catalyst include triethylamine, benzylmethylamine, methyltriethylammonium chloride, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, and triphenylphosphine. These catalysts may be used alone or in combination of two or more.

[0065] From the viewpoint of promoting the reaction between components (a) and (b), the amount of the catalyst used can be 0.01 to 10 parts by mass, 0.05 to 2 parts by mass, or 0.1 to 1 part by mass relative to 100 parts by mass of the total of components (a) and (b).

[0066] During the reaction between components (a) and (b), a polymerization inhibitor may be used to prevent polymerization during the reaction. Examples of polymerization inhibitors include hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, and gallol. These polymerization inhibitors may be used alone or in combination of two or more.

[0067] From the viewpoint of improving stability, the amount of the polymerization inhibitor used may be 0.01 to 1 part by mass, 0.02 to 0.8 part by mass, or 0.04 to 0.5 part by mass relative to 100 parts by mass of the total of components (a) and (b).

[0068] From the viewpoint of productivity, the reaction temperature of the components (a) and (b) may be 60 to 150°C, 80 to 120°C, or 90 to 110°C.

[0069] Component (A'), formed by reacting components (a) and (b), has hydroxyl groups formed by a ring-opening addition reaction between the epoxy groups of component (a) and the carboxyl groups of component (b). By further reacting component (c) with component (A'), an acid-modified vinyl-containing resin is obtained in which the hydroxyl groups of component (A') (including those originally present in component (a)) and the anhydride groups of component (c) are half-esterified.

[0070] Examples of component (c) include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, and itaconic anhydride. Among these, tetrahydrophthalic anhydride is preferred from the perspective of resolution. Component (c) may be used alone or in combination of two or more.

[0071] In the reaction of component (A') and component (c), for example, the acid value of component (A) can be adjusted by reacting 0.1 to 1.0 equivalents of component (c) per 1 equivalent of the hydroxyl groups in component (A').

[0072] From the viewpoint of productivity, the reaction temperature of the component (A') and the component (c) may be 50 to 150°C, 60 to 120°C, or 70 to 100°C.

[0073] If necessary, as the component (a), a portion of a hydrogenated bisphenol A epoxy resin may be used in combination, and a portion of a styrene-maleic acid-based resin such as a hydroxyethyl (meth)acrylate modified product of a styrene-maleic anhydride copolymer may also be used in combination.

[0074] From the perspective of suppressing the occurrence of undercuts and further improving adhesion to the copper substrate, thermal shock resistance, and resolution, it is preferable that component (A) includes component (A1). In particular, from the perspective of improving adhesion strength, it is more preferable that component (A1) and component (A2) are included.

[0075] When components (A1) and (A2) are used in combination as component (A), the mass ratio of (A1) / (A2) is not particularly limited, but from the perspective of improving the linearity of the resist pattern contour, non-adhesion resistance, and heat resistance, it can be 20 / 80 to 90 / 10, 30 / 70 to 80 / 20, 40 / 60 to 75 / 25, or 50 / 50 to 70 / 30.

[0076] The acid value of component (A) is not particularly limited. To improve the solubility of the unexposed portion in an alkaline aqueous solution, the acid value of component (A) may be 30 mgKOH / g or greater, 40 mgKOH / g or greater, or 50 mgKOH / g or greater. To improve the electrical properties of the cured film, the acid value of component (A) may be 150 mgKOH / g or less, 120 mgKOH / g or less, or 100 mgKOH / g or less.

[0077] The weight average molecular weight (Mw) of component (A) is not particularly limited. From the perspective of improving the adhesion of the cured film, the Mw of component (A) may be 3,000 or greater, 4,000 or greater, or 5,000 or greater. From the perspective of improving the resolution of the photosensitive layer, the Mw of component (A) may be 30,000 or less, 25,000 or less, or 18,000 or less.

[0078] Mw can be measured by gel permeation chromatography (GPC). For example, Mw can be measured under the following GPC conditions, and the value converted using a calibration curve of standard polystyrene can be used as Mw. The calibration curve can be created using a set of five samples ("PStQuick MP-H" and "PStQuick B," manufactured by Tosoh Corporation) as standard polystyrene. GPC apparatus: High-speed GPC apparatus "HCL-8320GPC" (manufactured by Tosoh Corporation) Detector: Differential refractometer or UV detector (manufactured by Tosoh Corporation) Column: TSKgel SuperMultipore HZ-H (column length: 15 cm, column inner diameter: 4.6 mm) (manufactured by Tosoh Corporation) Eluent: Tetrahydrofuran (THF) Measurement temperature: 40℃ Flow rate: 0.35mL / min Sample concentration: 10 mg / THF5 mL Injection volume: 20 μL

[0079] From the perspective of improving the heat resistance, electrical properties, and chemical resistance of the permanent resist, the content of component (A) in the photosensitive resin composition can be 20-70 mass %, 25-60 mass %, or 30-50 mass %, based on the total solid content of the photosensitive resin composition.

[0080] (Component (B): thermosetting resin) The photosensitive resin composition of this embodiment contains a thermosetting resin as component (B), which comprises a bisphenol-type epoxy compound having an average molecular weight of 360 or less (hereinafter sometimes referred to as "component (B1)"). The inclusion of component (B1) in the photosensitive resin composition of this embodiment maintains good resolution and improves the heat resistance and thermal shock resistance of the cured film (permanent resist) formed from the photosensitive resin composition.

[0081] Component (B1) is an epoxy compound synthesized by a condensation reaction between a bisphenol compound and epichlorohydrin. Examples of the bisphenol compound include bisphenol A, bisphenol F, and bisphenol S. Component (B1) contains as its main component a diglycidyl ether having a bisphenol skeleton (diglycidyl ether represented by the following formula (1)) in which 2 moles of epichlorohydrin are bonded to 1 mole of the bisphenol compound. [Chemistry 7]

[0082] In formula (1), X represents a methylene group (CH 2), an ethylene group (CH 2CH 2), an ethylene group (CH(CH 3)), a 1-methylethylene group (C(CH 3) 2), or a sulfonic group. From the viewpoint of improving developability, X is preferably a methylene group or a 1-methylethylene group.

[0083] Typical bisphenol-type epoxy compounds include polymers of bisphenol compounds and epichlorohydrin (e.g., oligomer components such as dimers and trimers). In contrast, the oligomer content of component (B1) is low. To further improve developability and thermal shock resistance, the content of the diglycidyl ether represented by formula (1) in component (B1) can be 94% by mass or greater, 96% by mass or greater, or 98% by mass or greater.

[0084] From the perspective of further improving heat resistance and thermal shock resistance, the average molecular weight of component (B1) may be 310-360, 315-359, 320-358, 325-357, or 330-356. The average molecular weight can be calculated, for example, by GPC (see Reports of the Central Customs Laboratory, No. 21, 1980, pp. 85-90, "Determination of the degree of polymerization of epoxy oligomers by GPC, NMR, etc.").

[0085] To further improve heat resistance and thermal shock resistance, the epoxy equivalent of component (B1) may be 150-182 g / eq, 154-181 g / eq, 160-180 g / eq, 162-179 g / eq, or 166-178 g / eq. The epoxy equivalent can be measured in accordance with JIS K 7236.

[0086] Component (B) may contain other thermosetting resins other than component (B1). Examples of other thermosetting resins include epoxy resins, phenolic resins, unsaturated imide resins, cyanate resins, isocyanate resins, benzophenone resins, cyclohexane resins, amino resins, unsaturated polyester resins, allyl resins, dicyclopentadiene resins, silicone resins, tris-imide resins, and melamine resins that do not have a bisphenol skeleton. Among these, epoxy resins that do not have a bisphenol skeleton are preferred from the perspective of further improving the heat resistance of the cured film. Examples of epoxy resins that do not have a bisphenol skeleton include novolac epoxy resins, dicyclopentadiene epoxy resins, hydrogenated bisphenol A epoxy resins, biphenyl epoxy resins, hydantoin epoxy resins, triglycidyl isocyanate, and dimethylol epoxy resins.

[0087] The content of component (B1) in component (B) may be 30% by mass or more, 50% by mass or more, or 60% by mass or more based on the total amount of component (B). When the content is 30% by mass or more, there is a tendency for better thermal shock resistance to be obtained.

[0088] The content of component (B) in the photosensitive resin composition can be 2-30% by mass, 5-25% by mass, 8-20% by mass, or 10-18% by mass, based on the total solid content of the photosensitive resin composition. When the content of component (B) is within the above range, the adhesion and heat resistance of the resulting cured film can be further improved while maintaining good developability.

[0089] (Component (C): photopolymerization initiator) The photopolymerization initiator as component (C) is not particularly limited as long as it can polymerize components (A) and (D). Components (C) may be used alone or in combination of two or more.

[0090] Examples of the component (C) include benzoin, benzoin methyl ether, benzoin isopropyl ether and other benzoin compounds; acetophenone compounds such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-benzyl-2-dimethylamino-1-(4-amino-phenyl)-butanone-1,2-methyl-[4-(methylthio)phenyl]-2-amino-1-propane, and N,N-dimethylaminoacetophenone; 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-anthraquinone, and 2-tert-anthraquinone. Anthraquinone compounds such as butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, and 2-aminoanthraquinone; thioxanthone compounds such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone; ketal compounds such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone compounds such as benzophenone, methyl benzophenone, 4,4'-dichlorobenzophenone, 4,4'-bis(diethylamino)benzophenone, Michelle's ketone, and 4-benzoyl-4'-methyldiphenyl sulfide; 2-(o-chlorophenyl)-4,5-diphenylimidazole diacetate imidazole compounds such as 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, 2,4-di(p-methoxyphenyl)-5-phenylimidazole dimer, 2-(2,4-dimethoxyphenyl)-4,5-diphenylimidazole dimer; acridine compounds such as 9-phenylacridine and 1,7-bis(9,9'-acridinyl)heptane; 2,4,6-triazine; Acyl phosphine oxide compounds such as methylbenzyldiphenylphosphine oxide; oxime ester compounds such as 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzoyl oxime), 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyl oxime), and 1-phenyl-1,2-propanedione-2-[O-(ethoxycarbonyl)oxime]; and tertiary amine compounds such as ethyl N,N-dimethylaminobenzoate, isopentyl N,N-dimethylaminobenzoate, amyl-4-dimethylaminobenzoate, triethylamine, and triethanolamine.

[0091] The content of component (C) in the photosensitive resin composition is not particularly limited and may be 0.2-15 mass %, 0.4-5 mass %, or 0.6-1.5 mass % based on the total solid content of the photosensitive resin composition.

[0092] (Component (D): photopolymerizable compound) From the perspective of improving the chemical resistance of the exposed area and increasing the difference in developer resistance between the exposed and unexposed areas, the photosensitive resin composition of this embodiment contains a photopolymerizable compound as component (D). Component (D) is not particularly limited, as long as it is a photopolymerizable compound having a photopolymerizable functional group and no acidic group. Examples of photopolymerizable functional groups include groups having ethylenically unsaturated bonds, such as vinyl, allyl, propargyl, butenyl, ethynyl, phenylethynyl, maleimide, naphthaleneimide, and (meth)acryloyl groups.

[0093] Examples of the component (D) include a photopolymerizable compound having one ethylenically unsaturated bond, a photopolymerizable compound having two ethylenically unsaturated bonds, and a photopolymerizable compound having three or more ethylenically unsaturated bonds.

[0094] Examples of photopolymerizable compounds having one ethylenically unsaturated bond include (meth)acrylic acid and alkyl (meth)acrylates. Examples of alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and hydroxyethyl (meth)acrylate.

[0095] Examples of the photopolymerizable compound having two ethylenically unsaturated bond groups include polyethylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, polypropylene glycol di(meth)acrylate, 2,2-bis(4-(meth)acryloyloxypolyethoxypolypropoxyphenyl)propane, and bisphenol A diglycidyl ether di(meth)acrylate.

[0096] Examples of the photopolymerizable compound having three or more ethylenically unsaturated bonds include (meth)acrylate compounds having a skeleton derived from trimethylolpropane, such as trimethylolpropane tri(meth)acrylate; (meth)acrylate compounds having a skeleton derived from tetramethylolmethane, such as tetramethylolmethane tri(meth)acrylate and tetramethylolmethane tetra(meth)acrylate; (meth)acrylate compounds having a skeleton derived from pentaerythritol, such as pentaerythritol tri(meth)acrylate and pentaerythritol tetra(meth)acrylate; (meth)acrylate compounds having a skeleton derived from dipentaerythritol, such as dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate; (meth)acrylate compounds having a skeleton derived from ditrimethylolpropane, such as ditrimethylolpropane tetra(meth)acrylate; and (meth)acrylate compounds having a skeleton derived from diglycerol.

[0097] Among these, from the viewpoint of improving the chemical resistance of the exposed portion and increasing the difference in developer resistance between the exposed portion and the unexposed portion, (meth)acrylate compounds having a skeleton derived from dipentatritol are preferred, and dipentatritol penta(meth)acrylate and dipentatritol hexa(meth)acrylate are more preferred.

[0098] The content of the component (D) may be 1 to 20 mass %, 2 to 15 mass %, or 3 to 10 mass % based on the total solid content of the photosensitive resin composition.

[0099] ((E) component: elastomer) The photosensitive resin composition of this embodiment, by including an elastomer as component (E), can suppress the reduction in flexibility and adhesive strength caused by deformation (internal stress) within the resin due to cure shrinkage of component (A). Component (E) contains an acrylic elastomer, thereby improving the heat resistance and impact resistance of the cured film formed from the photosensitive resin composition.

[0100] Acrylic elastomers can be synthesized by polymerizing (meth)acrylic compounds. Examples of (meth)acrylic compounds include (meth)acrylic acid, (meth)acrylates, and acrylonitrile.

[0101] Examples of the (meth)acrylate include methyl (meth)acrylate, (meth)acrylic acid, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, and 2-ethoxyethyl (meth)acrylate.

[0102] From the perspective of further improving developability, acrylic elastomers preferably contain carboxyl groups. Carboxyl groups can be introduced by polymerizing (meth)acrylic acid. The content of (meth)acrylic acid-based structural units in the acrylic resin can be 2-50% by mass, 5-30% by mass, 8-25% by mass, or 10-20% by mass. When the content of (meth)acrylic acid-based structural units is within the above ranges, developability and resolution tend to be improved.

[0103] From the perspective of further improving impact resistance, acrylic elastomers preferably contain n-butyl groups. n-Butyl groups can be introduced by polymerizing n-butyl (meth)acrylate. The content of n-butyl (meth)acrylate-based structural units in the acrylic elastomer can be 30-90% by mass, 40-85% by mass, 45-80% by mass, or 50-75% by mass. When the content of n-butyl (meth)acrylate-based structural units is within these ranges, resolution and impact resistance tend to be improved.

[0104] The weight-average molecular weight (Mw) of the acrylic elastomer can be 1,000 to 50,000, 2,000 to 40,000, 3,000 to 30,000, 5,000 to 20,000, or 8,000 to 18,000. When the Mw of the acrylic elastomer is within this range, compatibility with component (A) and developability of unexposed areas tend to be excellent, and resolution tends to be even better. The Mw of the acrylic elastomer can be measured by the GPC method described above.

[0105] The component (E) may also contain an elastomer other than an acrylic elastomer. Examples of the component (E) other than an acrylic elastomer include styrene elastomers, olefin elastomers, urethane elastomers, polyester elastomers, polyamide elastomers, and silicone elastomers.

[0106] Examples of styrene-based elastomers include styrene-butadiene-styrene blocked copolymers, styrene-isoprene-styrene blocked copolymers, styrene-ethylene-butylene-styrene blocked copolymers, and styrene-ethylene-propylene-styrene blocked copolymers. In addition to styrene, styrene-based elastomers can also include styrene derivatives such as α-methylstyrene, 3-methylstyrene, 4-propylstyrene, and 4-cyclohexylstyrene.

[0107] Examples of olefin-based elastomers include ethylene-propylene copolymers, ethylene-α-olefin copolymers, ethylene-α-olefin-non-conjugated diene copolymers, propylene-α-olefin copolymers, butene-α-olefin copolymers, ethylene-propylene-diene copolymers, copolymers of non-conjugated dienes such as dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene, ethylidene norbornene, butadiene, and isoprene with α-olefins, epoxy-modified polybutadiene, and carboxylic acid-modified butadiene-acrylonitrile copolymers.

[0108] The epoxy-modified polybutadiene preferably has a hydroxyl group at a molecular terminal, more preferably at both molecular terminals, and even more preferably only at both molecular terminals. The number of hydroxyl groups in the epoxy-modified polybutadiene may be one or more, preferably 1 to 5, more preferably 1 or 2, and even more preferably 2.

[0109] As the urethane elastomer, a compound composed of a hard segment containing a low molecular weight (short chain) diol and a diisocyanate and a soft segment containing a high molecular weight (long chain) diol and a diisocyanate can be used.

[0110] Examples of the short-chain diol include ethylene glycol, propylene glycol, 1,4-butanediol, and bisphenol A. The number average molecular weight of the short-chain diol is preferably 48 to 500.

[0111] Examples of long-chain diols include polypropylene glycol, polyoxytetramethylene glycol, poly(1,4-butylene adipate), poly(1,4-butylene ethyl adipate), polycaprolactone, poly(1,6-hexylene carbonate), and poly(1,6-hexylene-neopentyl adipate). The number average molecular weight of the long-chain diol is preferably 500 to 10,000.

[0112] As the polyester elastomer, a compound obtained by polycondensing a dicarboxylic acid or a derivative thereof with a diol compound or a derivative thereof can be used.

[0113] Examples of dicarboxylic acids include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalene dicarboxylic acid; aliphatic dicarboxylic acids having 2 to 20 carbon atoms such as adipic acid, sebacic acid, and dodecanedicarboxylic acid; and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. The dicarboxylic acids may be used alone or in combination of two or more.

[0114] Examples of the diol compound include aliphatic diols such as ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, and 1,10-decanediol; alicyclic diols such as 1,4-cyclohexanediol; and aromatic diols such as bisphenol A, bis-(4-hydroxyphenyl)methane, bis-(4-hydroxy-3-methylphenyl)propane, and resorcinol.

[0115] Polyester elastomers can be polyblock copolymers containing an aromatic polyester (e.g., polybutylene terephthalate) as the hard segment component and an aliphatic polyester (e.g., polytetramethylene glycol) as the soft segment component. Polyester elastomers are available in different grades depending on the type, ratio, and molecular weight of the hard and soft segments.

[0116] Polyamide elastomers are broadly classified into two types: polyether-blocked amides, which use polyamide in the hard segment and polyether or polyester in the soft segment, and polyetherester-blocked amides. Examples of polyamides include polyamide-6, polyamide-11, and polyamide-12. Examples of polyethers include polyoxyethylene glycol, polyoxypropylene glycol, and polytetramethylene glycol.

[0117] Silicone elastomers are compounds primarily composed of organopolysiloxanes. Examples of organopolysiloxanes include polydimethylsiloxane, polymethylphenylsiloxane, and polydiphenylsiloxane. Silicone elastomers can be compounds obtained by modifying a portion of an organopolysiloxane with a vinyl group, an alkoxy group, or the like.

[0118] The content of component (E) can be 1 to 40 parts by mass, 2 to 35 parts by mass, 3 to 30 parts by mass, or 4 to 15 parts by mass relative to 100 parts by mass of component (A). The content of component (E) can be 5 parts by mass or more, 8 parts by mass or more, or 10 parts by mass or more, or can be 40 parts by mass or less, 35 parts by mass or less, 30 parts by mass or less, or 25 parts by mass or less. When the content of component (E) is within the above range, the elastic modulus of the cured film in the high temperature range is lowered, and the unexposed portion is more easily eluted in the developer.

[0119] ((F) ingredient: inorganic filler) The photosensitive resin composition of this embodiment may further contain an inorganic filler as component (F). The inclusion of component (F) can enhance the adhesive strength and hardness of the permanent resist. Component (F) may be used alone or in combination of two or more.

[0120] Examples of the inorganic filler include silica, alumina, titanium dioxide, tantalum oxide, zirconium oxide, silicon nitride, barium titanate, barium carbonate, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, lead titanate, lead zirconate titanate, lead lanthanum zirconate titanate, gallium oxide, spinel, mullite, cordierite, talc, aluminum titanate, yttria-containing zirconium oxide, barium silicate, boron nitride, calcium carbonate, barium sulfate, calcium sulfate, zinc oxide, magnesium titanate, hydrotalcite, mica, calcined kaolin, and carbon.

[0121] To improve the heat resistance of the permanent resist, component (F) may include silicon dioxide. To improve the heat resistance and adhesive strength of the permanent resist, it may include barium sulfate, or both silicon dioxide and barium sulfate. To improve the dispersibility of the inorganic filler, an inorganic filler that has been surface-treated with alumina or an organosilane compound may be used.

[0122] From the viewpoint of resolution, the average particle size of the inorganic filler may be 0.01 to 5.0 μm, 0.05 to 3.0 μm, 0.1 to 2.0 μm, or 0.15 to 1.0 μm.

[0123] The average particle size of component (F) is the average particle size of the inorganic filler dispersed in the photosensitive resin composition and is measured as follows. First, the photosensitive resin composition is diluted 1000-fold with methyl ethyl ketone. The particles dispersed in the solvent are measured using a submicron particle analyzer (Beckman Coulter, Inc., product name: N5) in accordance with international standard ISO 13321 at a refractive index of 1.38. The average particle size is the particle size at 50% of the integrated value (volume basis) in the particle size distribution.

[0124] The content of component (F) can be 10-70% by mass, 15-60% by mass, or 20-50% by mass based on the total solid content of the photosensitive resin composition. When the content of component (E) is within the above range, the low thermal expansion coefficient, heat resistance, and film strength can be further improved.

[0125] When silicon dioxide is used as component (F), the silicon dioxide content can be 5-60% by mass, 10-40% by mass, or 15-30% by mass based on the total solid content of the photosensitive resin composition. When barium sulfate is used as component (F), the barium sulfate content can be 5-30% by mass, 8-25% by mass, or 10-20% by mass based on the total solid content of the photosensitive resin composition. When the silicon dioxide and barium sulfate contents are within these ranges, the composition tends to have a low thermal expansion coefficient, excellent solder heat resistance, and excellent adhesive strength.

[0126] ((G) ingredient: pigment) To improve the visibility and appearance of the manufacturing device, the photosensitive resin composition of this embodiment may further contain a pigment as component (G). Component (G) can be a colorant that develops a desired color when concealing wiring (conductor pattern), etc. Component (G) can be used alone or in combination of two or more.

[0127] Examples of the component (G) include phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, and naphthalene black.

[0128] From the perspective of facilitating identification of the manufacturing device and further concealing the wiring, the content of the component (G) may be 0.01 to 5.0 mass %, 0.03 to 3.0 mass %, or 0.05 to 2.0 mass % based on the total solid content in the photosensitive resin composition.

[0129] (Component (H): ion trapping agent) From the perspective of improving resist shape, adhesion, flowability, and reliability, the photosensitive resin composition of this embodiment may further contain an ion trapping agent as component (H). Component (H) is not particularly limited as long as it can trap ions in the ion trapping agent and has the function of trapping at least one of cations and anions.

[0130] In this embodiment, the trapped ions are ions such as sodium (Na+), chloride (Cl-), bromide (Br-), and copper (Cu+, Cu2+) ions, which are introduced into a composition that reacts with light, electron beams, and changes its solubility in the solvent. By trapping these ions, electrical insulation and electrical corrosion resistance are improved.

[0131] The component (H) preferably comprises at least one ion trapping agent selected from the group consisting of Zr (zirconium), Bi (bismuth), Mg (magnesium), and Al (aluminum). The component (H) may be used alone or in combination of two or more.

[0132] Examples of the component (H) include cation trapping agents that trap cations, anion trapping agents that trap anions, and ion trapping agents that trap both cations and anions.

[0133] Examples of the cation scavenger include inorganic ion exchangers of metal oxides such as zirconium phosphate, zirconium tungstate, zirconium molybdate, zirconium tungstate, zirconium antimonate, zirconium selenate, zirconium tellurate, zirconium silicate, zirconium phosphosilicate, and zirconium polyphosphate.

[0134] Examples of the anion scavenger include inorganic ion exchangers such as bismuth oxide hydrate and hydrotalcites.

[0135] Examples of two-ion scavengers include inorganic ion exchangers of metal hydrous oxides such as alumina hydrate and zirconium oxide hydrate. Commercially available two-ion scavengers include IXE-1320 (Mg and Al-containing compound), IXE-600 (Bi-containing compound), IXE-633 (Bi-containing compound), IXE-680 (Bi-containing compound), IXE-6107 (Zr and Bi-containing compound), IXE-6136 (Zr and Bi-containing compound), IXEPLAS-A1 (Zr, Mg and Al-containing compound), IXEPLAS-A2 (Zr, Mg and Al-containing compound), and IXEPLAS-B1 (Zr and Bi-containing compound) manufactured by Toagosei Co., Ltd.

[0136] Component (H) can be used in granular form. From the perspective of improving insulation properties, the average particle size of component (H) can be 5 μm or less, 3 μm or less, or 2 μm or less, or can be 0.1 μm or greater. The average particle size of component (H) refers to the particle size of particles dispersed in the photosensitive resin composition and can be measured using the same method as for measuring the average particle size of component (F).

[0137] When the photosensitive resin composition contains component (H), its content is not particularly limited. From the perspective of improving electrical insulation and electrical corrosion resistance, it can be 0.05 to 10% by mass, 0.1 to 5% by mass, or 0.2 to 1% by mass based on the total solid content of the photosensitive resin composition.

[0138] ((I) component: silane coupling agent) The photosensitive resin composition of this embodiment may further contain a silane coupling agent as component (I). Component (I) can be a known silane coupling agent. Component (I) can improve the adhesion between electronic components and substrates, and is particularly effective when the substrate contains silicon (e.g., a glass substrate, a silicon wafer, an epoxy resin-impregnated glass cloth substrate, etc.).

[0139] Examples of the silane coupling agent include alkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane; (meth)acryloxypropyltrimethoxysilane, (meth)acryloxypropylmethyldimethoxysilane, and other (meth)acrylyl group-containing alkoxysilanes; amine alkoxysilanes such as γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and 3-triethoxysilyl-N-(1,3-dimethylbutylene)propylamine; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropyltrimethoxysilane. Alkoxysilanes containing a glycidoxy group such as triethoxysilane, glycidoxypropylmethyldiethoxysilane, and glycidoxypropylmethyldiisopropenoxysilane; alkoxysilanes containing alicyclic epoxy groups such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; alkoxysilanes containing urea groups such as 3-ureidopropyltriethoxysilane; alkoxysilanes containing mercapto groups such as 3-mercaptopropyltrimethoxysilane and 3-mercaptopropylmethyldimethoxysilane; alkoxysilanes containing carbamate groups such as triethoxysilylpropylethylcarbamate; and alkoxysilanes containing polyacid anhydride groups such as 3-(triethoxysilyl)propylsuccinic anhydride. Silane coupling agents can be used alone or in combination of two or more.

[0140] From the perspective of further improving adhesion, component (I) preferably includes a silane coupling agent containing a (meth)acryl group. Using a silane coupling agent containing a (meth)acryl group maintains the heat resistance of the permanent resist and prevents bleed-out from the composition. In this specification, a silane coupling agent containing a (meth)acryl group is not included in component (D).

[0141] Examples of commercially available silane coupling agents having a (meth)acryl group include KBM-502, KBM-503, KBE-502, KBE-503, and KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0142] The content of component (I) can be 0.1-10% by mass, 0.5-5% by mass, or 1-3% by mass based on the total solid content of the photosensitive resin composition. When the content of component (I) is within the above range, excellent adhesion to the silicon wafer and excellent resolution tend to be achieved.

[0143] (Curing Agent) In order to further improve the heat resistance, adhesion, chemical resistance, and other properties of the cured film, the photosensitive resin composition of this embodiment may contain a curing agent. The curing agent may be used alone or in combination of two or more.

[0144] Examples of curing agents include imidazole compounds, guanamine compounds, amine compounds, and trisinium compounds. Examples of imidazole compounds include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenylimidazole, and 2-phenyl-4-methyl-5-hydroxymethylimidazole. Examples of guanamine compounds include acetoguanamine and benzoguanamine. Examples of amine compounds include diaminodiphenylmethane, m-phenylenediamine, m-xylenediamine, diaminodiphenylsulfonium, dicyandiamide, urea, urea derivatives, melamine, and polybasic hydrazides. Examples of trisinium compounds include ethyldiamino-s-trisinium, 2,4-diamino-s-trisinium, and 2,4-diamino-6-xylyl-s-trisinium.

[0145] From the viewpoint of improving the reliability of the cured film, the content of the curing agent may be 0.01 to 20 mass %, 0.05 to 10 mass %, or 0.1 to 5 mass % based on the total solid content of the photosensitive resin composition.

[0146] (Other ingredients) The photosensitive resin composition of this embodiment may further contain various additives as needed. Examples of these additives include polymerization inhibitors such as hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, and gallol; thickeners such as organic clay and montmorillonite; silicone-based, fluorine-based, and vinyl resin-based defoamers; and flame retardants such as brominated epoxy compounds, acid-modified brominated epoxy compounds, antimony compounds, phosphate ester compounds, aromatic condensed phosphate esters, and halogen-containing condensed phosphate esters.

[0147] (Solvent) The photosensitive resin composition of this embodiment contains a solvent for dissolving and dispersing the components, and thus can be easily coated on a substrate to form a coating film with uniform thickness.

[0148] Examples of the solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; glycol ethers such as methyl celulose, butyl celulose, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, and triethylene glycol monoethyl ether; esters such as ethyl acetate, butyl acetate, butyl celulose acetate, and carbitol acetate; aliphatic hydrocarbons such as octane and decane; and petroleum-based solvents such as petroleum ether, naphtha, hydrogenated naphtha, and solvent naphtha. These solvents may be used alone or in combination of two or more.

[0149] The amount of the solvent blended is not particularly limited, and the proportion of the solvent in the photosensitive resin composition can be 10-50 mass %, 20-40 mass %, or 25-35 mass %.

[0150] The photosensitive resin composition of this embodiment can be prepared by uniformly mixing the above-mentioned components using a roll mill, a bead mill, or the like.

[0151] [Photosensitive element] The photosensitive element of this embodiment comprises a support film and a photosensitive layer comprising the above-described photosensitive resin composition. FIG1 schematically illustrates a cross-sectional view of the photosensitive element of this embodiment. As shown in FIG1 , the photosensitive element 1 comprises a support film 10 and a photosensitive layer 20 formed on the support film 10.

[0152] The photosensitive element 1 can be manufactured by coating the photosensitive resin composition of this embodiment on a support film 10 by a known method such as reverse roll coating, gravure roll coating, comma coating, or curtain coating, and then drying the coating to form a photosensitive layer 20 .

[0153] Examples of the support film include polyester films such as polyethylene terephthalate and polybutylene terephthalate, and polyolefin films such as polypropylene and polyethylene. The thickness of the support film can be, for example, 5 to 100 μm. The thickness of the photosensitive layer can be, for example, 5 to 50 μm, 5 to 40 μm, or 10 to 30 μm. The surface roughness of the support film is not particularly limited; the arithmetic mean roughness (Ra) can be 1000 nm or less, 500 nm or less, or 250 nm or less.

[0154] The coating can be dried using hot air, far infrared radiation, or near infrared radiation. The drying temperature can be 60-120°C, 70-110°C, or 80-100°C. The drying time can be 1-60 minutes, 2-30 minutes, or 5-20 minutes.

[0155] A protective film 30 covering the photosensitive layer 20 may be further provided on the photosensitive layer 20. The photosensitive element 1 may also have the protective film 30 formed on the surface opposite to the surface of the photosensitive layer 20 that contacts the support film 10. For example, a polymer film such as polyethylene or polypropylene may be used as the protective film 30.

[0156] [Printed wiring board] The printed wiring board of this embodiment includes a permanent resist containing a cured product of the photosensitive resin composition of this embodiment.

[0157] The method for manufacturing a printed wiring board according to this embodiment includes the steps of forming a photosensitive layer on a substrate using the above-mentioned photosensitive resin composition or photosensitive element, exposing and developing the photosensitive layer to form a resist pattern, and curing the resist pattern to form a permanent resist. An example of each step is described below.

[0158] First, a substrate such as a copper-clad laminate is prepared, and a photosensitive layer is formed on the substrate. The photosensitive layer can also be formed by coating a photosensitive resin composition on the substrate and drying it. Examples of methods for coating the photosensitive resin composition include screen printing, spraying, roller coating, curtain coating, and electrostatic coating. The drying temperature can be 60-120°C, 70-110°C, or 80-100°C. The drying time can be 1-7 minutes, 1-6 minutes, or 2-5 minutes. The thickness of the photosensitive layer is preferably 5 μm or greater, but can also be 10-200 μm, 15-150 μm, 20-100 μm, or 23-50 μm.

[0159] The photosensitive layer can also be formed by peeling off the protective film from the photosensitive element and laminating the photosensitive layer on the substrate. As a method for laminating the photosensitive layer, for example, a method of heat lamination using a laminator can be mentioned.

[0160] Next, the negative film is brought into direct contact with the photosensitive layer or through a support film and exposed to active light. Examples of active light include electron beams, ultraviolet rays, and X-rays, with ultraviolet rays being preferred. Light sources include low-pressure mercury lamps, high-pressure mercury lamps, ultrahigh-pressure mercury lamps, and halogen lamps. The exposure dose can be 10-2000 mJ / cm², 100-1500 mJ / cm², or 300-1000 mJ / cm².

[0161] After exposure, the unexposed areas are removed with a developer to form a resist pattern. Examples of development methods include immersion and spraying. Examples of developer solutions include aqueous alkaline solutions such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, and tetramethylammonium hydroxide.

[0162] A patterned cured film (permanent resist) can be formed by performing at least one of post-exposure and post-heating on the resist pattern. The exposure dose of the post-exposure can be 100-5000 mJ / cm2, 500-2000 mJ / cm2, or 700-1500 J / cm2. The heating temperature of the post-heating can be 100-200°C, 120-180°C, or 135-165°C. The heating time of the post-heating can be 5 minutes to 12 hours, 10 minutes to 6 hours, or 30 minutes to 2 hours.

[0163] The permanent resist of this embodiment can be used as an interlayer insulating layer or surface protective layer for semiconductor devices. Semiconductor devices and electronic devices incorporating such semiconductor devices can be manufactured, each having an interlayer insulating layer or surface protective layer formed from a cured film of the photosensitive resin composition. Semiconductor devices may include, for example, memory devices or packages having multilayer wiring structures or redistribution structures. Examples of electronic devices include mobile phones, smartphones, tablet computers, personal computers, and hard drive suspensions. A patterned cured film formed from the photosensitive resin composition of this embodiment can provide semiconductor devices and electronic devices with excellent reliability. [Example]

[0164] The present disclosure is further described in detail below with reference to examples, but the present disclosure is not limited to these examples.

[0165] (Synthesis example 1) 350 parts by mass of a bisphenol F novolac epoxy resin (DIC Corporation, product name "EXA-7376," a bisphenol F novolac epoxy resin having a structural unit in which Y3 and Y4 are glycidyl groups and R12 is a hydrogen atom in formula (II), epoxy equivalent: 186), 70 parts by mass of acrylic acid, 0.5 parts by mass of methylhydroquinone, and 120 parts by mass of carbitol acetate were stirred and mixed at 90°C. The mixture was cooled to 60°C, 2 parts by mass of triphenylphosphine was added, and the mixture was reacted at 100°C until the acid value of the solution reached 1 mgKOH / g or less. 98 parts by mass of tetrahydrophthalic anhydride (THPAC) and 85 parts by mass of carbitol acetate were added to the reaction mixture, and the mixture was reacted at 80°C for 6 hours. Thereafter, the reaction solution was cooled to room temperature to obtain a solution of acid-modified epoxy acrylate (A-1) as the component (A) (solid content concentration: 73% by mass).

[0166] (Synthesis example 2) To a 100 mL three-necked flask equipped with a stirrer, nitrogen inlet tube, and thermometer, 70 g of ethyl lactate, 13.4 g of methyl acrylate, 22.5 g of n-butyl acrylate, 2.0 g of acrylic acid, and 3.0 g of azobisisobutyronitrile were added. The mixture was stirred at approximately 160 rpm at room temperature while nitrogen gas was flowed at 400 mL / min for 30 minutes to remove dissolved oxygen from the flask. The nitrogen flow was then stopped, the flask sealed, and the temperature was raised to 65°C in a thermostatic water bath over approximately 25 minutes. A polymerization reaction was carried out by maintaining the same temperature for 10 hours, yielding an acrylic elastomer (E-1). The Mw of E-1 was approximately 10,000.

[0167] (Synthesis example 3) A polymerization reaction was carried out according to the same procedure as for the synthesis of E-1, except that 70 g of ethyl lactate, 2.8 g of methyl acrylate, 13.3 g of n-butyl acrylate, 2.4 g of acrylic acid, and 1.0 g of azobisisobutyronitrile were added to obtain an acrylic elastomer (E-2). The Mw of E-2 was approximately 15,000.

[0168] The following materials were prepared as components (A) to (I). A-1: Acid-modified epoxy acrylate (A-1) of Synthesis Example 1 B-1: Bisphenol F epoxy resin (manufactured by NIPPON STEEL Chemical & Material Co., Ltd., trade name "YDF-8170C," average molecular weight: 310-330, epoxy equivalent: 155-165) B-2: Bisphenol A epoxy resin (manufactured by NIPPON STEEL Chemical & Material Co., Ltd., trade name "YD-8125," average molecular weight: 336-356, epoxy equivalent: 168-178) B-3: Bisphenol A epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name "jER828," average molecular weight: 368-388, epoxy equivalent: 184-194) B-4: Phenol novolac epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name "RE-306", average molecular weight: 400, epoxy equivalent: 170-181) C-1: 2-Methyl-[4-(methylthio)phenyl]-1-propanone (manufactured by IGM Resins BV, product name "Omirad 907") C-2: 2,4-Diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd., product name "DETX-S") C-3:4,4'-bis(diethylamino)benzophenone (EAB) C-4: Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(0-acetyl oxime) (manufactured by BASF Japan Ltd., product name "Irgacure OXE02") D-1: Dipentatriol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., product name "DPHA") E-1: Acrylic elastomer (E-1) of Synthesis Example 2 E-2: Acrylic elastomer (E-2) of Synthesis Example 3 F-1: Silica (manufactured by Denka Company Limited, product name "SFP20M", average particle size: 0.3 μm) F-2: Barium sulfate (manufactured by Sakai Chemical Industry Co., Ltd., product name "B-34", average particle size: 0.3 μm) G-1: Phthalocyanine pigment (manufactured by Sanyo Color Works, Ltd.) H-1: Zwitterion scavenger containing Zr, Mg, and Al (manufactured by Toagosei Company, Limited, product name "IXEPLAS-A2", average particle size: 0.2 μm, Zr compound content: 20-30% by mass) I-1: 3-Methacryloyloxypropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "KBM-503")

[0169] [Photosensitive resin composition] The components were blended in the amounts (parts by mass, based on solid content) listed in Table 1 or Table 2 and kneaded using a three-roll mill. Carbitol acetate was then added to achieve a solid content concentration of 70% by mass to prepare a photosensitive resin composition.

[0170] [Photosensitive element] A 25μm-thick polyethylene terephthalate film (TOYOBO FILM SOLUTIONS, product name "G2-25") was prepared as a support film. A solution prepared by diluting a photosensitive resin composition with methyl ethyl ketone was applied to the support film to a thickness of 25μm after drying. The film was then dried at 75°C for 30 minutes using a hot air convection dryer to form a photosensitive layer. Next, a polyethylene film (TAMAPOLY CO., LTD., product name "NF-15") was laminated as a protective film to the surface opposite the side in contact with the support film of the photosensitive layer, resulting in a photosensitive element.

[0171] (resolution) A 0.6mm-thick copper-clad laminate (MCL-E-67, manufactured by Showa Denko Materials Co., Ltd.) was prepared. The protective film was peeled off from the photosensitive element, and the photosensitive layer was laminated onto the copper-clad laminate using a press-type vacuum laminator (MVLP-500, manufactured by Meiki Co., Ltd.) at a pressure of 0.4 MPa, a hot plate temperature of 80°C, a vacuuming time of 25 seconds, and a lamination press time of 25 seconds to obtain a laminate. Next, a negative mask with an opening pattern of a predetermined size (opening diameters: 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 150, and 200 μm) was placed in close contact with the support film of the laminate. The photosensitive layer was exposed using an ultraviolet exposure device (manufactured by OAK Co., Ltd., product name "EXM-1201") at an exposure dose sufficient to achieve 13 fully cured steps on a grid (manufactured by Showa Denko Materials Co., Ltd.). The support film was then peeled from the photosensitive layer, and spray development was performed using a 1% by mass sodium carbonate aqueous solution for 60 seconds at a pressure of 1.765 × 10⁵ Pa to dissolve and develop the unexposed areas. Next, the developed photosensitive layer was exposed to 2000 mJ / cm² using an ultraviolet exposure device and then heated at 170°C for 1 hour to produce a test piece having a cured film with an opening pattern of a specified size formed on a copper-clad laminate. These test pieces were observed using an optical microscope and evaluated according to the following criteria. A: The minimum opening size is 30 μm or less. B: The minimum opening size is more than 30 μm and is 50 μm or less. C: The minimum opening size exceeds 50 μm.

[0172] (Resist Pattern Shape) The test piece was cast with an embedding resin ("jER828," manufactured by Mitsubishi Chemical Corporation, as the epoxy resin, and triethylenetetramine as the curing agent) and fully cured. The specimen was then polished using a grinder ("Refine Polisher," manufactured by Refine Tech Co., Ltd.), and a cross-section of the opening pattern of the cured film was obtained. The cross-section of the obtained opening pattern was observed using a metallographic microscope and evaluated according to the following criteria. A: No undercut or missing resist upper portion was observed, and the linearity of the pattern outline was good. B: Undercut or missing part of the resist top is confirmed, or the linearity of the pattern outline is poor.

[0173] (Thermal shock resistance) Test pieces produced for resolution evaluation were subjected to a temperature cycle test, with one cycle consisting of 30 minutes at -65°C and 30 minutes at 150°C. The test pieces were observed visually and under an optical microscope at 1000 and 2000 cycles, and evaluated according to the following criteria. A: No cracks were observed in 2000 cycles. B: No cracks were observed in 1000 cycles, but cracks were observed in 2000 cycles. C: Generation of cracks was observed in 1000 cycles.

[0174] (Heat resistance) Test pieces produced for resolution evaluation were placed in a 150°C environment. After 1000 hours and 2000 hours, the test pieces were observed visually and under an optical microscope, and evaluated according to the following criteria. A: No cracks were observed within 2000 hours. B: No cracks were observed within 1000 hours, but cracks were observed within 2000 hours. C: Cracks were observed within 1000 hours.

[0175] (Adhesion) A laminate with a photosensitive layer was produced using the same procedures as for the laminate produced in the resolution evaluation, except that a 6-inch silicon wafer (manufactured by ELECTRONICS AND MATERIALS CORPORATION) was used instead of a copper-clad laminate substrate. This laminate was fully exposed using an i-ray exposure system (manufactured by USHIO INC., trade name "UX-2240SM-XJ-01") at 500 mJ / cm². The support film was then peeled from the photosensitive layer, and the photosensitive layer was further exposed using an ultraviolet exposure system at 2000 mJ / cm². The layer was then heated at 170°C for one hour, forming a cured film of the photosensitive resin composition on the silicon wafer. An Al pin with epoxy adhesive (manufactured by PHOTOTECHNICA Co., Ltd., trade name "P / N 901106," bonding portion diameter: 2.7 mm) was then placed vertically on the cured film and heated at 150°C for 1 hour to obtain a test piece. The pin on the test piece was secured to the chuck of a thin film adhesion strength tester (manufactured by PHOTOTECHNICA Co., Ltd.), applying a force perpendicular to the cured film. The adhesion of the cured film to the silicon wafer was evaluated according to the following criteria. A: There is no peeling at the interface between the cured film and the silicon wafer, and the epoxy adhesive is coagulated and destroyed. B: Peeling at the interface between the cured film and the silicon wafer.

[0176] [Table 1] Example 1 2 3 4 5 6 A A-1 35 35 35 35 35 35 B B-1 13.1 - - - - - B-2 - 13.1 13.1 8.7 5 13.1 B-3 - - - - - - B-4 - - - 4.4 8.1 - C C-1 0.9 0.9 0.9 0.9 0.9 0.9 C-2 0.1 0.1 0.1 0.1 0.1 0.1 C-3 0.1 0.1 0.1 0.1 0.1 0.1 C-4 0.1 0.1 0.1 0.1 0.1 0.1 D D-1 5.2 5.2 5.2 5.2 5.2 5.2 E E-1 8 8 - 8 8 8 E-2 - - 8 - - - F F-1 17.5 17.5 17.5 17.5 17.5 17.5 F-2 13.1 13.1 13.1 13.1 13.1 】3.1 G G-1 1.3 1.3 1.3 1.3 1.3 1.3 H H-1 0.4 0.4 0.4 0.4 0.4 0.4 I I-1 2 2 2 2 2 - Resolution A A A A A A Resist pattern shape A A A A A A Thermal shock resistance A A A A A A Heat resistance A A A A A A Adhesion A A A A A B

[0177] [Table 2] Comparative Example 1 2 3 4 5 A A-1 35 35 35 35 35 B B-1 - - - - - B-2 13.1 - - - - B-3 - 13.1 - 8.7 8.7 B-4 - - 13.1 4.4 4.4 C C-1 0.9 0.9 0.9 0.9 0.9 C-2 0.1 0.1 0.1 0.1 0.1 C-3 0.1 0.1 0.1 0.1 0.1 C-4 0.1 0.1 0.1 0.1 0.1 D D-1 5.2 5.2 5.2 5.2 5.2 E E-1 - 8 8 - -8 E-2 - - - - - F F-1 17.5 17.5 17.5 17.5 17.5 F-2 13.1 13.1 13.1 13.1 13.1 G G-1 1.3 1.3 1.3 1.3 1.3 H H-1 0.4 0.4 0.4 0.4 0.4 I I-1 2 2 2 2 - Resolution A B B A A Resist pattern shape A B B A A Heat shock resistance B C A C B Heat resistance B C B C B Continuity A A A A B

[0178] 1: Photosensitive element 10: Support film 20: Photosensitive layer 30: Protective film

Claims

1. A photosensitive resin composition comprising (A) an acid-modified vinyl resin, (B) a thermosetting resin, (C) a photopolymerization initiator, (D) a photopolymerizable compound, and (E) an elastomer, wherein the thermosetting resin comprises a bisphenol-type epoxy compound with an average molecular weight of 360 or less, the elastomer comprises an acrylic elastomer, the acrylic elastomer has a weight average molecular weight of 5,000 to 20,000, the content of the thermosetting resin is 5 to 25% by mass based on the total solid content of the photosensitive resin composition, and the content of the elastomer (E) is 1 to 40 parts by mass relative to 100 parts by mass of the acid-modified vinyl resin (A).

2. The photosensitive resin composition as claimed in claim 1, wherein the aforementioned acrylic elastomer has a carboxyl group.

3. The photosensitive resin composition as described in claim 2, wherein the aforementioned acrylic elastomer further comprises n-butyl.

4. The photosensitive resin composition as described in claim 1, further comprising (I) a silane coupling agent.

5. The photosensitive resin composition as described in claim 1, further comprising (F) inorganic filler.

6. A photosensitive element comprising a support film and a photosensitive layer formed on the support film, the photosensitive layer comprising the photosensitive resin composition described in any one of claims 1 to 5.

7. A printed wiring board comprising a permanent resist of a cured composition comprising any one of claims 1 to 5.

8. A method for manufacturing a printed wiring board, comprising: a step of forming a photosensitive layer on a substrate using a photosensitive resin composition described in any one of claims 1 to 5; a step of exposing and developing the aforementioned photosensitive layer to form a resist pattern; and a step of curing the aforementioned resist pattern to form a permanent resist.

9. A method for manufacturing a printed wiring board, comprising: a step of forming a photosensitive layer on a substrate using a photosensitive element as described in claim 6; a step of exposing and developing the aforementioned photosensitive layer to form a resist pattern; and a step of curing the aforementioned resist pattern to form a permanent resist.

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